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Attempted synthesis of ortho-phenylene phosphino-tritylium cations.

ABSTRACT: With the synthesis of ortho-phenylene phosphino-tritylium cations as an objective, we generated (2-lithiophenyl)diphenylphosphine and (2-lithiophenyl)di-isopropylphosphine and allowed these organolithium reagents to react with benzophenone. The resulting phosphino-triarylcarbinols were allowed to react with HBF4 in the presence of trifluoroacetic anhydride in order to generate the corresponding cations. Instead of the targeted ortho-phenylene phosphino-tritylium, the cations formed in these reactions were identified as the four-membered phosphonium species 7,7-bis(phenyl)-8,8-bis(phenyl)-7-phosphoniabicyclo[4.2.0]octa-1,3,5-triene (3+) and 7,7-bis(phenyl)-8,8-bis(isopropyl)-7-phosphoniabicyclo[4.2.0]octa-1,3,5-triene (4+), which were both isolated as tetrafluoroborate salts. The structure of these compounds has been confirmed by X-ray analysis. These new cations are thermally unstable and isomerize into the corresponding 5,10-dihydro-5,5-diphenyl-10-phenyl-acridophosphinium (5+) and 5,10-dihydro-5,5-di(isopropyl)-10-phenyl-acridophosphinium (6+) as tetrafluoroborate salts. These reactions suggest the involvement of ortho-phenylene phosphino-tritylium cations, which would be obtained by dissociation of the R3P+-CAr3 bonds in 4+ and 5+This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

SUBMITTER: Chansaenpak K

PROVIDER: S-EPMC5540840 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Attempted synthesis of ortho-phenylene phosphino-tritylium cations.

Chansaenpak Kantapat K Yang Mengxi M Gabbaï François P FP

Philosophical transactions. Series A, Mathematical, physical, and engineering sciences 20170801 2101

With the synthesis of ortho-phenylene phosphino-tritylium cations as an objective, we generated (2-lithiophenyl)diphenylphosphine and (2-lithiophenyl)di-isopropylphosphine and allowed these organolithium reagents to react with benzophenone. The resulting phosphino-triarylcarbinols were allowed to react with HBF4 in the presence of trifluoroacetic anhydride in order to generate the corresponding cations. Instead of the targeted ortho-phenylene phosphino-tritylium, the cat ...[more]

PMID: 28739965

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Project description:The self-assembly of foldamers into macrocycles is a simple approach to non-biological higher-order structure. Previous work on the co-assembly of ortho-phenylene foldamers with rod-shaped linkers has shown that folding and self-assembly affect each other; that is, the combination leads to new emergent behavior, such as access to otherwise unfavorable folding states. To this point this relationship has been passive. Here, we demonstrate control of self-assembly by manipulating the foldamers' conformational energy surfaces. A series of o-phenylene decamers and octamers have been assembled into macrocycles using imine condensation. Product distributions were analyzed by gel-permeation chromatography and molecular geometries extracted from a combination of NMR spectroscopy and computational chemistry. The assembly of o-phenylene decamers functionalized with alkoxy groups or hydrogens gives both [2 + 2] and [3 + 3] macrocycles. The mixture results from a subtle balance of entropic and enthalpic effects in these systems: the smaller [2 + 2] macrocycles are entropically favored but require the oligomer to misfold, whereas a perfectly folded decamer fits well within the larger [3 + 3] macrocycle that is entropically disfavored. Changing the substituents to fluoro groups, however, shifts assembly quantitatively to the [3 + 3] macrocycle products, even though the structural changes are well-removed from the functional groups directly participating in bond formation. The electron-withdrawing groups favor folding in these systems by strengthening arene-arene stacking interactions, increasing the enthalpic penalty to misfolding. The architectural changes are substantial even though the chemical perturbation is small: analogous o-phenylene octamers do not fit within macrocycles when perfectly folded, and quantitatively misfold to give small macrocycles regardless of substitution. Taken together, these results represent both a high level of structural control in structurally complex foldamer systems and the demonstration of large-amplitude structural changes as a consequence of a small structural effects.

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Attempted synthesis of ortho-phenylene phosphino-tritylium cations.

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Attempted synthesis of <i>ortho</i>-phenylene phosphino-tritylium cations.

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